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Enhanced low-temperature proton conductivity in hydrogen-intercalated brownmillerite oxide

An Author Correction to this article was published on 07 August 2023

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Solid oxide ionic conductors are employed in a wide range of energy-conversion applications, such as electrolytes in fuel cells. Typically, conventional ionic conductors based on metal oxides require elevated temperatures above approximately 500 °C to activate ionic transport, but the ability to operate at lower temperature could avoid mechanical instability and operating complexities. Here we report a solid oxide proton conductor, HSrCoO2.5, which shows unusually high proton conductivity between 40 °C and 140 °C. The proton conductivity was between 0.028 S cm−1 to 0.33 S cm−1 in this temperature range, with an ionic activation energy of approximately 0.27 eV. Combining experimental results and first-principles calculations, we attribute these intriguing properties to the high proton concentration and the well-ordered oxygen vacancy channels granted by the hydrogen-intercalated brownmillerite crystalline structure. Our results open the possibility of using solid oxide materials as the proton-conducting electrolytes in low-temperature devices.

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Fig. 1: Design principle for proton electrolyte HSrCoO2.5.
Fig. 2: Proton conductivity measurement.
Fig. 3: Noble metal catalysis-induced hydrogen intercalation in strontium cobaltite thin films.
Fig. 4: Calculated hydrogen migration path within the H-SCO.
Fig. 5: Proof-of-concept in-planar dual-chamber SOFC with the H-SCO as proton electrolyte.

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All data supporting the findings of this study are available within the paper and Supplementary Information files. Source data in the Main Text and Supplementary Information are provided with this paper. Source data are provided with this paper.

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We thank Z.-P. Shao, Y. Zhou and C.-C. Duan for helpful discussions and critical reading of the manuscript and Y. Shi and T. Liu for experimental assistance. This study was financially supported by the Basic Science Center Project of NFSC (grant number 51788104, P.Y. and C.-W.N.), the Ministry of Science and Technology of China (grant number 2021YFE0107900, P.Y.), the Beijing Nature Science Foundation (grant number Z200007, P.Y.), the National Key R&D Program of China (grant number 2021YFA1400100, S.Z., and 2021YFA1400300, P.Y.), the National Natural Science Foundation of China (grant nos. 52025024 and 51872155, P.Y.), the Beijing Advanced Innovation Center for Future Chip (ICFC, P.Y. and S.Z.) and Major Science and Technology Project of Precious Metal Materials Genome Engineering in Yunnan Province (grant number 2019ZE001-1, J.W.). N.L. acknowledges support from the National Natural Science Foundation of China (grant number 11974401), CAS Project for Young Scientists in Basic Research (grant number YSBR-047) and the Strategic Priority Research Program of Chinese Academy of Sciences of China (grant number XDB33000000).

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Authors and Affiliations



P.Y. conceived the project and designed the experiments. N.L., Yongshun.Wu., S.L., X.C., M.Z., Z.L. and Jianbing.Zhang. fabricated the thin films. N.L., Y.Wang. and H.L. carried out ILG, structural, optical and compositional characterization. N.L., C.L. and X.L. performed the impedance spectroscopy, d.c. measurement and dual-chamber fuel cell characterization and test, with help from H.L., D.Z., X.C., S.Y., M.W. and J.M. Z.Z, S.Q., B.Z. and J.R. performed the theoretical analysis and calculations, under the supervision of J.W. Q.H., J.G. and K.D. performed the soft X-ray absorption measurements. Jingzhao.Zhang., S.C.T., J.Zhu., Yang.Wu., S.Z., Y.T. and C.-W.N. discussed the results. N.L. and P.Y. wrote the manuscript, and all authors discussed results and commented on the manuscript.

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Correspondence to Jian Wu or Pu Yu.

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Nature Energy thanks Shriram Ramanathan and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–25, Notes 1–6 and Tables 1 and 2.

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Lu, N., Zhang, Z., Wang, Y. et al. Enhanced low-temperature proton conductivity in hydrogen-intercalated brownmillerite oxide. Nat Energy 7, 1208–1216 (2022).

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